The title compounds,
N-[5-(4-chlorophenyl)furan-2-ylmethyl]-4-methyl-
N-(prop-2-ynyl)benzenesulfonamide, (I
a), and
N-[5-(2-chlorophenyl)furan-2-ylmethyl]-4-methyl-
N-(prop-2-ynyl)benzenesulfonamide, (I
b), both C
21H
18ClNO
3S, have isomorphous crystal structures. The crystal packing is mainly determined by intermolecular C—H
O and C—H
π interactions. These interactions are very similar in (I
a) and (I
b). Additional intermolecular C—H
Cl interactions appear less important and are different in (I
a) and (I
b). The different positions of the Cl atoms result in small variations of the crystal packing of the two compounds.
Supporting information
CCDC references: 173374; 173375
Synthesis of (Ia): 5-(4-chlorophenyl)furan-2-carbaldehyde (705 mg, 3.41 mmol),
prop-2-ynylamine (188 mg, 3.41 mmol) and MgSO4 (800 mg, 6.56 mmol), were
stirred in dichloromethane. After 24 h the solvent was removed in
vacuo, the residue taken up in methanol and NaBH4 (70.3 mg, 1.86 mmol)
added. After 16 h an aqueous workup and column chromatography on silica gel
(hexane/ethyl acetate, 3:1) provided 351 mg (42%) of
[5-(4-chlorophenyl)furan-2-ylmethyl]prop-2-ynylamine. The latter amine (300 mg, 1.22 mmol), p-toluenesulfonyl chloride (233 mg, 1.22 mmol),
triethylamine (234 mg, 1.22 mmol) and
4-N,N-dimethylaminopyridine (7.5 mg, 61.4 µmol) in
dichloromethane were stirred for 16 h. After aqueous workup and column
chromatography on silica gel (hexane/ethyl acetate/dichloromethane, 20:1:1)
176 mg (36%) (Ia) were obtained as colourless crystals with a melting point of
415–417 K. Single crystals were obtained from a hexane/dichloromethane
mixture at 277 K. Synthesis of (Ib): 5-(2-chlorophenyl)furan-2-carbaldehyde
(1.00 g, 4.84 mmol), prop-2-ynylamine (265 mg, 4.84 mmol), MgSO4 (1.00 g,
83.1 mmol) and NaBH4 (91.6 mg, 2.42 mmol) were treated as described above
for (Ia). Column chromatography on silica gel (hexane/ethyl
acetate/dichloromethane, 5:1:1) provided
[5-(2-chlorophenyl)furan-2-ylmethyl]prop-2-ynylamine (572 mg, 48%). From the
latter amine (572 mg, 2.33 mmol), p-toluenesulfonyl chloride (533 mg,
2.80 mmol), triethylamine (290 mg, 2.87 mmol) and
4-N,N-dimethylaminopyridine (14.2 mg, 283 mmol) by the method
described for (Ia) after column chromatography (hexane/ethyl
acetate/dichloromethane, 20:1:1) 531 mg (57%) of (Ib) were obtained as
colourless crystals with a melting point of 404–405 K. Single crystals were
obtained from a hexane/dichloromethane mixture at 277 K.
The H atoms were taken from a difference Fourier synthesis. They were refined
with fixed individual displacement parameters [U(H) = 1.2Ueq(C) and
U(H) = 1.5Ueq(Cmethyl)] using a riding model with fixed distances:
H—C(methyl) = 0.98 Å, H—C(secondary) = 0.99 Å,
H—C(phenyl) = 0.95 Å and H—C(alkyne) = 0.95 Å. Torsion
angles about the C—C bond of the methyl groups were refined.
For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1996); software used to prepare material for publication: CIF in SHELXL97.
(Ia)
N-[5-(4-Chlorophenyl)furan-2-ylmethyl]-4-methyl-N-prop-2-
ynylbenzenesulfonamide
top
Crystal data top
C21H18ClNO3S | Z = 2 |
Mr = 399.87 | F(000) = 416 |
Triclinic, P1 | Dx = 1.405 Mg m−3 |
a = 7.5309 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.5789 (14) Å | Cell parameters from 139 reflections |
c = 13.893 (2) Å | θ = 3–23° |
α = 80.234 (9)° | µ = 0.33 mm−1 |
β = 82.252 (14)° | T = 140 K |
γ = 73.959 (10)° | Plate, colorless |
V = 945.1 (3) Å3 | 0.50 × 0.24 × 0.08 mm |
Data collection top
SIEMENS SMART CCD diffractometer | 5805 independent reflections |
Radiation source: normal-focus sealed tube | 4256 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scans | θmax = 30.9°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −10→10 |
Tmin = 0.923, Tmax = 0.974 | k = −13→13 |
19065 measured reflections | l = −20→20 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | H atom parameters constrained |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.04P)2 + 0.5P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
5805 reflections | Δρmax = 0.51 e Å−3 |
246 parameters | Δρmin = −0.40 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0049 (13) |
Crystal data top
C21H18ClNO3S | γ = 73.959 (10)° |
Mr = 399.87 | V = 945.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5309 (16) Å | Mo Kα radiation |
b = 9.5789 (14) Å | µ = 0.33 mm−1 |
c = 13.893 (2) Å | T = 140 K |
α = 80.234 (9)° | 0.50 × 0.24 × 0.08 mm |
β = 82.252 (14)° | |
Data collection top
SIEMENS SMART CCD diffractometer | 5805 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 4256 reflections with I > 2σ(I) |
Tmin = 0.923, Tmax = 0.974 | Rint = 0.037 |
19065 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.107 | H atom parameters constrained |
S = 1.03 | Δρmax = 0.51 e Å−3 |
5805 reflections | Δρmin = −0.40 e Å−3 |
246 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl | 1.26308 (6) | 0.81634 (5) | 0.09648 (3) | 0.03122 (12) | |
S | 0.41927 (5) | 0.56063 (5) | 0.71345 (3) | 0.02126 (11) | |
O1 | 0.53892 (15) | 0.82692 (12) | 0.44086 (8) | 0.0195 (2) | |
O2 | 0.53879 (17) | 0.63523 (15) | 0.74386 (9) | 0.0314 (3) | |
O3 | 0.48167 (17) | 0.40663 (14) | 0.70762 (9) | 0.0293 (3) | |
N | 0.37457 (18) | 0.64124 (15) | 0.60098 (9) | 0.0186 (3) | |
C1 | 0.8842 (2) | 0.80993 (19) | 0.32764 (12) | 0.0236 (3) | |
H1 | 0.8832 | 0.7781 | 0.3963 | 0.028* | |
C2 | 1.0529 (2) | 0.78976 (19) | 0.26962 (12) | 0.0247 (4) | |
H2 | 1.1662 | 0.7436 | 0.2980 | 0.030* | |
C3 | 1.0526 (2) | 0.83802 (18) | 0.16996 (12) | 0.0216 (3) | |
C4 | 0.8884 (2) | 0.90250 (19) | 0.12682 (12) | 0.0240 (3) | |
H4 | 0.8905 | 0.9338 | 0.0581 | 0.029* | |
C5 | 0.7212 (2) | 0.92085 (18) | 0.18510 (12) | 0.0222 (3) | |
H5 | 0.6082 | 0.9643 | 0.1558 | 0.027* | |
C6 | 0.7168 (2) | 0.87615 (17) | 0.28648 (11) | 0.0186 (3) | |
C7 | 0.5393 (2) | 0.89978 (17) | 0.34629 (11) | 0.0190 (3) | |
C8 | 0.3657 (2) | 0.98183 (19) | 0.32933 (13) | 0.0259 (4) | |
H8 | 0.3287 | 1.0434 | 0.2704 | 0.031* | |
C9 | 0.2493 (2) | 0.95794 (19) | 0.41718 (13) | 0.0271 (4) | |
H9 | 0.1195 | 1.0000 | 0.4278 | 0.032* | |
C10 | 0.3591 (2) | 0.86414 (18) | 0.48223 (12) | 0.0205 (3) | |
C11 | 0.3233 (2) | 0.80345 (18) | 0.58662 (12) | 0.0213 (3) | |
H11A | 0.3956 | 0.8380 | 0.6277 | 0.026* | |
H11B | 0.1900 | 0.8401 | 0.6082 | 0.026* | |
C12 | 0.2690 (2) | 0.57503 (18) | 0.54707 (12) | 0.0208 (3) | |
H12A | 0.2940 | 0.6046 | 0.4758 | 0.025* | |
H12B | 0.3140 | 0.4669 | 0.5604 | 0.025* | |
C13 | 0.0666 (2) | 0.61795 (18) | 0.57363 (12) | 0.0224 (3) | |
C14 | −0.0937 (3) | 0.6524 (2) | 0.59811 (14) | 0.0309 (4) | |
H14 | −0.2229 | 0.6801 | 0.6178 | 0.037* | |
C15 | 0.2091 (2) | 0.59566 (18) | 0.78959 (11) | 0.0196 (3) | |
C16 | 0.1103 (2) | 0.49034 (19) | 0.81408 (13) | 0.0251 (4) | |
H16 | 0.1590 | 0.3961 | 0.7939 | 0.030* | |
C17 | −0.0608 (3) | 0.5242 (2) | 0.86845 (13) | 0.0290 (4) | |
H17 | −0.1278 | 0.4515 | 0.8861 | 0.035* | |
C18 | −0.1363 (2) | 0.6615 (2) | 0.89759 (12) | 0.0250 (4) | |
C19 | −0.0337 (3) | 0.7649 (2) | 0.87259 (13) | 0.0284 (4) | |
H19 | −0.0828 | 0.8593 | 0.8924 | 0.034* | |
C20 | 0.1387 (3) | 0.7334 (2) | 0.81937 (13) | 0.0274 (4) | |
H20 | 0.2077 | 0.8049 | 0.8035 | 0.033* | |
C21 | −0.3248 (3) | 0.6975 (2) | 0.95450 (14) | 0.0357 (5) | |
H21A | −0.4212 | 0.7098 | 0.9106 | 0.054* | |
H21B | −0.3429 | 0.7887 | 0.9820 | 0.054* | |
H21C | −0.3327 | 0.6175 | 1.0078 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0225 (2) | 0.0338 (2) | 0.0322 (2) | −0.00639 (18) | 0.00871 (17) | −0.00078 (18) |
S | 0.01355 (19) | 0.0270 (2) | 0.02171 (19) | −0.00347 (15) | −0.00091 (14) | −0.00279 (15) |
O1 | 0.0150 (5) | 0.0210 (6) | 0.0209 (5) | −0.0040 (4) | 0.0013 (4) | −0.0020 (4) |
O2 | 0.0199 (6) | 0.0484 (8) | 0.0302 (7) | −0.0145 (6) | −0.0036 (5) | −0.0072 (6) |
O3 | 0.0222 (6) | 0.0263 (7) | 0.0319 (7) | 0.0032 (5) | −0.0012 (5) | −0.0003 (5) |
N | 0.0151 (6) | 0.0209 (7) | 0.0201 (6) | −0.0053 (5) | 0.0012 (5) | −0.0046 (5) |
C1 | 0.0197 (8) | 0.0291 (9) | 0.0203 (7) | −0.0052 (7) | −0.0008 (6) | −0.0020 (6) |
C2 | 0.0176 (8) | 0.0275 (9) | 0.0268 (8) | −0.0037 (7) | −0.0012 (7) | −0.0016 (7) |
C3 | 0.0188 (8) | 0.0208 (8) | 0.0245 (8) | −0.0069 (6) | 0.0047 (6) | −0.0037 (6) |
C4 | 0.0264 (9) | 0.0249 (9) | 0.0201 (8) | −0.0087 (7) | 0.0003 (7) | 0.0002 (6) |
C5 | 0.0194 (8) | 0.0217 (8) | 0.0245 (8) | −0.0053 (6) | −0.0024 (6) | −0.0007 (6) |
C6 | 0.0180 (8) | 0.0160 (7) | 0.0222 (7) | −0.0062 (6) | 0.0008 (6) | −0.0031 (6) |
C7 | 0.0188 (8) | 0.0184 (8) | 0.0208 (7) | −0.0070 (6) | 0.0000 (6) | −0.0030 (6) |
C8 | 0.0199 (8) | 0.0249 (9) | 0.0285 (9) | −0.0024 (7) | −0.0013 (7) | 0.0021 (7) |
C9 | 0.0165 (8) | 0.0261 (9) | 0.0335 (9) | −0.0017 (7) | 0.0016 (7) | 0.0000 (7) |
C10 | 0.0149 (7) | 0.0188 (8) | 0.0272 (8) | −0.0044 (6) | 0.0030 (6) | −0.0052 (6) |
C11 | 0.0178 (8) | 0.0206 (8) | 0.0250 (8) | −0.0048 (6) | 0.0046 (6) | −0.0073 (6) |
C12 | 0.0194 (8) | 0.0214 (8) | 0.0225 (8) | −0.0056 (6) | 0.0002 (6) | −0.0064 (6) |
C13 | 0.0223 (8) | 0.0231 (8) | 0.0232 (8) | −0.0073 (7) | −0.0042 (6) | −0.0030 (6) |
C14 | 0.0202 (9) | 0.0390 (11) | 0.0348 (10) | −0.0095 (8) | −0.0017 (7) | −0.0064 (8) |
C15 | 0.0160 (8) | 0.0242 (8) | 0.0181 (7) | −0.0045 (6) | −0.0012 (6) | −0.0031 (6) |
C16 | 0.0259 (9) | 0.0197 (8) | 0.0283 (8) | −0.0062 (7) | 0.0041 (7) | −0.0042 (6) |
C17 | 0.0286 (9) | 0.0290 (10) | 0.0316 (9) | −0.0146 (8) | 0.0067 (7) | −0.0057 (7) |
C18 | 0.0217 (8) | 0.0339 (10) | 0.0186 (7) | −0.0061 (7) | 0.0007 (6) | −0.0054 (7) |
C19 | 0.0308 (10) | 0.0261 (9) | 0.0282 (9) | −0.0069 (7) | 0.0059 (7) | −0.0108 (7) |
C20 | 0.0310 (10) | 0.0278 (9) | 0.0275 (8) | −0.0145 (8) | 0.0054 (7) | −0.0099 (7) |
C21 | 0.0247 (10) | 0.0516 (13) | 0.0308 (10) | −0.0102 (9) | 0.0073 (8) | −0.0132 (9) |
Geometric parameters (Å, º) top
Cl—C3 | 1.7466 (17) | C9—H9 | 0.9500 |
S—O3 | 1.4321 (13) | C10—C11 | 1.486 (2) |
S—O2 | 1.4352 (13) | C11—H11A | 0.9900 |
S—N | 1.6553 (14) | C11—H11B | 0.9900 |
S—C15 | 1.7640 (16) | C12—C13 | 1.477 (2) |
O1—C10 | 1.3726 (19) | C12—H12A | 0.9900 |
O1—C7 | 1.3792 (18) | C12—H12B | 0.9900 |
N—C11 | 1.479 (2) | C13—C14 | 1.179 (2) |
N—C12 | 1.482 (2) | C14—H14 | 0.9500 |
C1—C2 | 1.393 (2) | C15—C16 | 1.385 (2) |
C1—C6 | 1.396 (2) | C15—C20 | 1.390 (2) |
C1—H1 | 0.9500 | C16—C17 | 1.388 (2) |
C2—C3 | 1.383 (2) | C16—H16 | 0.9500 |
C2—H2 | 0.9500 | C17—C18 | 1.386 (3) |
C3—C4 | 1.386 (2) | C17—H17 | 0.9500 |
C4—C5 | 1.387 (2) | C18—C19 | 1.390 (3) |
C4—H4 | 0.9500 | C18—C21 | 1.510 (2) |
C5—C6 | 1.400 (2) | C19—C20 | 1.387 (2) |
C5—H5 | 0.9500 | C19—H19 | 0.9500 |
C6—C7 | 1.458 (2) | C20—H20 | 0.9500 |
C7—C8 | 1.354 (2) | C21—H21A | 0.9800 |
C8—C9 | 1.428 (2) | C21—H21B | 0.9800 |
C8—H8 | 0.9500 | C21—H21C | 0.9800 |
C9—C10 | 1.350 (2) | | |
| | | |
O3—S—O2 | 120.34 (8) | O1—C10—C11 | 117.06 (14) |
O3—S—N | 105.87 (7) | N—C11—C10 | 111.58 (13) |
O2—S—N | 105.35 (7) | N—C11—H11A | 109.3 |
O3—S—C15 | 108.96 (8) | C10—C11—H11A | 109.3 |
O2—S—C15 | 107.86 (8) | N—C11—H11B | 109.3 |
N—S—C15 | 107.85 (7) | C10—C11—H11B | 109.3 |
C10—O1—C7 | 106.64 (12) | H11A—C11—H11B | 108.0 |
C11—N—C12 | 114.77 (13) | C13—C12—N | 113.53 (13) |
C11—N—S | 115.84 (10) | C13—C12—H12A | 108.9 |
C12—N—S | 116.88 (11) | N—C12—H12A | 108.9 |
C2—C1—C6 | 121.01 (15) | C13—C12—H12B | 108.9 |
C2—C1—H1 | 119.5 | N—C12—H12B | 108.9 |
C6—C1—H1 | 119.5 | H12A—C12—H12B | 107.7 |
C3—C2—C1 | 118.93 (16) | C14—C13—C12 | 177.67 (18) |
C3—C2—H2 | 120.5 | C13—C14—H14 | 180.0 |
C1—C2—H2 | 120.5 | C16—C15—C20 | 120.58 (15) |
C2—C3—C4 | 121.36 (15) | C16—C15—S | 120.26 (13) |
C2—C3—Cl | 119.52 (13) | C20—C15—S | 119.04 (13) |
C4—C3—Cl | 119.12 (13) | C15—C16—C17 | 119.14 (16) |
C3—C4—C5 | 119.24 (15) | C15—C16—H16 | 120.4 |
C3—C4—H4 | 120.4 | C17—C16—H16 | 120.4 |
C5—C4—H4 | 120.4 | C18—C17—C16 | 121.60 (16) |
C4—C5—C6 | 120.83 (15) | C18—C17—H17 | 119.2 |
C4—C5—H5 | 119.6 | C16—C17—H17 | 119.2 |
C6—C5—H5 | 119.6 | C17—C18—C19 | 118.10 (16) |
C1—C6—C5 | 118.60 (15) | C17—C18—C21 | 120.82 (17) |
C1—C6—C7 | 121.73 (14) | C19—C18—C21 | 121.08 (17) |
C5—C6—C7 | 119.67 (15) | C20—C19—C18 | 121.48 (16) |
C8—C7—O1 | 109.76 (14) | C20—C19—H19 | 119.3 |
C8—C7—C6 | 133.33 (15) | C18—C19—H19 | 119.3 |
O1—C7—C6 | 116.91 (14) | C19—C20—C15 | 119.08 (16) |
C7—C8—C9 | 106.70 (15) | C19—C20—H20 | 120.5 |
C7—C8—H8 | 126.6 | C15—C20—H20 | 120.5 |
C9—C8—H8 | 126.6 | C18—C21—H21A | 109.5 |
C10—C9—C8 | 106.78 (15) | C18—C21—H21B | 109.5 |
C10—C9—H9 | 126.6 | H21A—C21—H21B | 109.5 |
C8—C9—H9 | 126.6 | C18—C21—H21C | 109.5 |
C9—C10—O1 | 110.11 (14) | H21A—C21—H21C | 109.5 |
C9—C10—C11 | 132.76 (15) | H21B—C21—H21C | 109.5 |
| | | |
O3—S—N—C11 | −174.73 (11) | C8—C9—C10—C11 | 176.52 (17) |
O2—S—N—C11 | −46.23 (13) | C7—O1—C10—C9 | −0.54 (18) |
C15—S—N—C11 | 68.75 (13) | C7—O1—C10—C11 | −177.66 (13) |
O3—S—N—C12 | 45.15 (13) | C12—N—C11—C10 | −61.85 (17) |
O2—S—N—C12 | 173.65 (11) | S—N—C11—C10 | 157.20 (11) |
C15—S—N—C12 | −71.36 (13) | C9—C10—C11—N | 123.2 (2) |
C6—C1—C2—C3 | 0.7 (3) | O1—C10—C11—N | −60.47 (18) |
C1—C2—C3—C4 | −1.5 (3) | C11—N—C12—C13 | −59.37 (18) |
C1—C2—C3—Cl | 178.95 (13) | S—N—C12—C13 | 81.16 (16) |
C2—C3—C4—C5 | 0.9 (3) | O3—S—C15—C16 | −14.78 (16) |
Cl—C3—C4—C5 | −179.53 (13) | O2—S—C15—C16 | −146.99 (14) |
C3—C4—C5—C6 | 0.5 (3) | N—S—C15—C16 | 99.69 (15) |
C2—C1—C6—C5 | 0.6 (2) | O3—S—C15—C20 | 169.26 (13) |
C2—C1—C6—C7 | −179.22 (15) | O2—S—C15—C20 | 37.05 (16) |
C4—C5—C6—C1 | −1.2 (2) | N—S—C15—C20 | −76.27 (15) |
C4—C5—C6—C7 | 178.62 (15) | C20—C15—C16—C17 | 0.3 (3) |
C10—O1—C7—C8 | 0.89 (18) | S—C15—C16—C17 | −175.60 (14) |
C10—O1—C7—C6 | −179.41 (13) | C15—C16—C17—C18 | 1.0 (3) |
C1—C6—C7—C8 | 166.11 (19) | C16—C17—C18—C19 | −1.3 (3) |
C5—C6—C7—C8 | −13.7 (3) | C16—C17—C18—C21 | 178.42 (17) |
C1—C6—C7—O1 | −13.5 (2) | C17—C18—C19—C20 | 0.5 (3) |
C5—C6—C7—O1 | 166.63 (14) | C21—C18—C19—C20 | −179.26 (17) |
O1—C7—C8—C9 | −0.87 (19) | C18—C19—C20—C15 | 0.7 (3) |
C6—C7—C8—C9 | 179.49 (17) | C16—C15—C20—C19 | −1.1 (3) |
C7—C8—C9—C10 | 0.5 (2) | S—C15—C20—C19 | 174.83 (14) |
C8—C9—C10—O1 | 0.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 0.95 | 2.64 | 3.519 (2) | 153 |
C4—H4···Clii | 0.95 | 3.01 | 3.821 (2) | 144 |
C12—H12B···O1iii | 0.99 | 2.73 | 3.703 (2) | 169 |
C14—H14···O2iv | 0.95 | 2.41 | 3.227 (3) | 144 |
C17—H17···Cliii | 0.95 | 2.97 | 3.900 (2) | 165 |
C19—H19···Clv | 0.95 | 3.05 | 3.977 (2) | 166 |
C21—H21A···O2iv | 0.98 | 2.61 | 3.423 (2) | 140 |
C16—H16···Cg2iii | 0.95 | 2.60 | 3.457 (2) | 150 |
C20—H20···C5v | 0.95 | 2.86 | 3.733 (2) | 154 |
C1—H1···C14vi | 0.95 | 2.87 | 3.812 (2) | 174 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z; (v) −x+1, −y+2, −z+1; (vi) x+1, y, z. |
(Ib)
N-[5-(2-Chlorophenyl)furan-2-ylmethyl]-4-methyl-N-prop-2-
ynylbenzenesulfonamide
top
Crystal data top
C21H18ClNO3S | Z = 2 |
Mr = 399.87 | F(000) = 416 |
Triclinic, P1 | Dx = 1.422 Mg m−3 |
a = 7.6526 (13) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.679 (2) Å | Cell parameters from 160 reflections |
c = 13.6308 (19) Å | θ = 3–23° |
α = 79.910 (13)° | µ = 0.34 mm−1 |
β = 75.152 (13)° | T = 140 K |
γ = 74.435 (12)° | Plate, colorless |
V = 934.0 (3) Å3 | 0.50 × 0.16 × 0.12 mm |
Data collection top
SIEMENS SMART CCD diffractometer | 6133 independent reflections |
Radiation source: normal-focus sealed tube | 4738 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scans | θmax = 31.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −11→10 |
Tmin = 0.921, Tmax = 0.960 | k = −14→13 |
19124 measured reflections | l = −18→20 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | H atom parameters constrained |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.03P)2 + 0.52P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
6133 reflections | Δρmax = 0.36 e Å−3 |
246 parameters | Δρmin = −0.47 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0045 (12) |
Crystal data top
C21H18ClNO3S | γ = 74.435 (12)° |
Mr = 399.87 | V = 934.0 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.6526 (13) Å | Mo Kα radiation |
b = 9.679 (2) Å | µ = 0.34 mm−1 |
c = 13.6308 (19) Å | T = 140 K |
α = 79.910 (13)° | 0.50 × 0.16 × 0.12 mm |
β = 75.152 (13)° | |
Data collection top
SIEMENS SMART CCD diffractometer | 6133 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 4738 reflections with I > 2σ(I) |
Tmin = 0.921, Tmax = 0.960 | Rint = 0.029 |
19124 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.094 | H atom parameters constrained |
S = 1.04 | Δρmax = 0.36 e Å−3 |
6133 reflections | Δρmin = −0.47 e Å−3 |
246 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl | 0.65820 (6) | 0.99972 (4) | 0.11706 (3) | 0.03172 (10) | |
S | 0.37642 (4) | 0.55893 (4) | 0.72833 (3) | 0.02020 (9) | |
O1 | 0.54390 (13) | 0.81985 (10) | 0.44958 (7) | 0.0193 (2) | |
O2 | 0.48538 (14) | 0.63515 (13) | 0.76035 (8) | 0.0296 (2) | |
O3 | 0.44409 (14) | 0.40722 (11) | 0.71881 (8) | 0.0275 (2) | |
N | 0.35159 (15) | 0.63846 (12) | 0.61347 (9) | 0.0189 (2) | |
C1 | 0.90423 (19) | 0.79566 (16) | 0.34722 (11) | 0.0232 (3) | |
H1 | 0.8716 | 0.7645 | 0.4181 | 0.028* | |
C2 | 1.0903 (2) | 0.76800 (18) | 0.29754 (12) | 0.0285 (3) | |
H2 | 1.1829 | 0.7180 | 0.3344 | 0.034* | |
C3 | 1.1414 (2) | 0.81313 (17) | 0.19423 (12) | 0.0283 (3) | |
H3 | 1.2690 | 0.7959 | 0.1604 | 0.034* | |
C4 | 1.0056 (2) | 0.88333 (15) | 0.14089 (11) | 0.0259 (3) | |
H4 | 1.0396 | 0.9131 | 0.0698 | 0.031* | |
C5 | 0.81893 (19) | 0.91053 (14) | 0.19106 (11) | 0.0205 (3) | |
C6 | 0.76272 (18) | 0.86853 (14) | 0.29554 (10) | 0.0181 (3) | |
C7 | 0.56929 (18) | 0.89571 (14) | 0.35321 (10) | 0.0178 (3) | |
C8 | 0.4037 (2) | 0.98215 (16) | 0.33891 (12) | 0.0256 (3) | |
H8 | 0.3819 | 1.0459 | 0.2795 | 0.031* | |
C9 | 0.2688 (2) | 0.95870 (17) | 0.43025 (12) | 0.0275 (3) | |
H9 | 0.1399 | 1.0041 | 0.4433 | 0.033* | |
C10 | 0.35837 (18) | 0.86026 (15) | 0.49440 (11) | 0.0206 (3) | |
C11 | 0.29922 (19) | 0.79840 (15) | 0.60215 (11) | 0.0218 (3) | |
H11A | 0.3580 | 0.8340 | 0.6464 | 0.026* | |
H11B | 0.1627 | 0.8316 | 0.6250 | 0.026* | |
C12 | 0.26103 (19) | 0.57047 (15) | 0.55732 (11) | 0.0208 (3) | |
H12A | 0.3000 | 0.5996 | 0.4832 | 0.025* | |
H12B | 0.3044 | 0.4643 | 0.5695 | 0.025* | |
C13 | 0.0566 (2) | 0.60995 (16) | 0.58748 (11) | 0.0231 (3) | |
C14 | −0.1072 (2) | 0.64134 (18) | 0.61597 (13) | 0.0307 (3) | |
H14 | −0.2386 | 0.6665 | 0.6388 | 0.037* | |
C15 | 0.15477 (18) | 0.58783 (14) | 0.81087 (10) | 0.0181 (3) | |
C16 | 0.05678 (19) | 0.48039 (15) | 0.83493 (11) | 0.0224 (3) | |
H16 | 0.1112 | 0.3891 | 0.8103 | 0.027* | |
C17 | −0.1221 (2) | 0.50822 (16) | 0.89562 (11) | 0.0243 (3) | |
H17 | −0.1887 | 0.4343 | 0.9132 | 0.029* | |
C18 | −0.20563 (19) | 0.64170 (15) | 0.93115 (10) | 0.0209 (3) | |
C19 | −0.1045 (2) | 0.74817 (16) | 0.90564 (12) | 0.0266 (3) | |
H19 | −0.1598 | 0.8401 | 0.9291 | 0.032* | |
C20 | 0.0753 (2) | 0.72198 (16) | 0.84652 (11) | 0.0252 (3) | |
H20 | 0.1436 | 0.7948 | 0.8305 | 0.030* | |
C21 | −0.4010 (2) | 0.67046 (17) | 0.99532 (12) | 0.0284 (3) | |
H21A | −0.4896 | 0.6868 | 0.9514 | 0.043* | |
H21B | −0.4240 | 0.7562 | 1.0301 | 0.043* | |
H21C | −0.4164 | 0.5871 | 1.0463 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0343 (2) | 0.0335 (2) | 0.01961 (17) | 0.00061 (15) | −0.00544 (14) | 0.00306 (14) |
S | 0.01403 (15) | 0.02546 (17) | 0.01882 (16) | −0.00380 (12) | −0.00073 (12) | −0.00216 (12) |
O1 | 0.0169 (4) | 0.0206 (5) | 0.0171 (4) | −0.0041 (3) | 0.0008 (3) | −0.0003 (4) |
O2 | 0.0189 (5) | 0.0470 (7) | 0.0268 (6) | −0.0134 (5) | −0.0040 (4) | −0.0067 (5) |
O3 | 0.0220 (5) | 0.0246 (5) | 0.0281 (6) | 0.0024 (4) | −0.0017 (4) | −0.0008 (4) |
N | 0.0173 (5) | 0.0203 (5) | 0.0176 (5) | −0.0057 (4) | 0.0006 (4) | −0.0027 (4) |
C1 | 0.0197 (6) | 0.0288 (7) | 0.0194 (6) | −0.0052 (5) | −0.0020 (5) | −0.0023 (5) |
C2 | 0.0192 (7) | 0.0353 (8) | 0.0301 (8) | −0.0040 (6) | −0.0051 (6) | −0.0052 (6) |
C3 | 0.0199 (7) | 0.0298 (8) | 0.0319 (8) | −0.0083 (6) | 0.0056 (6) | −0.0078 (6) |
C4 | 0.0296 (7) | 0.0219 (7) | 0.0214 (7) | −0.0090 (6) | 0.0056 (6) | −0.0013 (5) |
C5 | 0.0238 (6) | 0.0164 (6) | 0.0192 (6) | −0.0045 (5) | −0.0020 (5) | −0.0011 (5) |
C6 | 0.0190 (6) | 0.0162 (6) | 0.0181 (6) | −0.0055 (5) | −0.0004 (5) | −0.0030 (5) |
C7 | 0.0199 (6) | 0.0167 (6) | 0.0159 (6) | −0.0061 (5) | −0.0014 (5) | −0.0009 (5) |
C8 | 0.0208 (7) | 0.0263 (7) | 0.0251 (7) | −0.0036 (5) | −0.0030 (5) | 0.0034 (6) |
C9 | 0.0164 (6) | 0.0300 (7) | 0.0303 (8) | −0.0028 (5) | 0.0002 (6) | 0.0002 (6) |
C10 | 0.0172 (6) | 0.0194 (6) | 0.0229 (7) | −0.0064 (5) | 0.0027 (5) | −0.0039 (5) |
C11 | 0.0208 (6) | 0.0193 (6) | 0.0219 (7) | −0.0062 (5) | 0.0042 (5) | −0.0046 (5) |
C12 | 0.0201 (6) | 0.0222 (6) | 0.0195 (6) | −0.0051 (5) | −0.0017 (5) | −0.0048 (5) |
C13 | 0.0240 (7) | 0.0243 (7) | 0.0216 (7) | −0.0084 (5) | −0.0053 (5) | −0.0002 (5) |
C14 | 0.0225 (7) | 0.0381 (9) | 0.0314 (8) | −0.0086 (6) | −0.0063 (6) | −0.0012 (7) |
C15 | 0.0156 (6) | 0.0220 (6) | 0.0153 (6) | −0.0046 (5) | −0.0007 (5) | −0.0018 (5) |
C16 | 0.0230 (7) | 0.0189 (6) | 0.0227 (7) | −0.0058 (5) | 0.0007 (5) | −0.0025 (5) |
C17 | 0.0225 (7) | 0.0243 (7) | 0.0256 (7) | −0.0111 (5) | 0.0013 (5) | −0.0030 (5) |
C18 | 0.0184 (6) | 0.0257 (7) | 0.0165 (6) | −0.0054 (5) | −0.0005 (5) | −0.0012 (5) |
C19 | 0.0283 (7) | 0.0223 (7) | 0.0261 (7) | −0.0075 (6) | 0.0051 (6) | −0.0082 (6) |
C20 | 0.0268 (7) | 0.0245 (7) | 0.0245 (7) | −0.0126 (6) | 0.0042 (6) | −0.0074 (6) |
C21 | 0.0203 (7) | 0.0331 (8) | 0.0272 (8) | −0.0058 (6) | 0.0032 (6) | −0.0047 (6) |
Geometric parameters (Å, º) top
Cl—C5 | 1.7425 (15) | C9—H9 | 0.9500 |
S—O2 | 1.4351 (11) | C10—C11 | 1.4890 (19) |
S—O3 | 1.4372 (11) | C11—H11A | 0.9900 |
S—N | 1.6528 (12) | C11—H11B | 0.9900 |
S—C15 | 1.7603 (13) | C12—C13 | 1.472 (2) |
O1—C10 | 1.3723 (16) | C12—H12A | 0.9900 |
O1—C7 | 1.3821 (16) | C12—H12B | 0.9900 |
N—C12 | 1.4807 (18) | C13—C14 | 1.184 (2) |
N—C11 | 1.4819 (18) | C14—H14 | 0.9500 |
C1—C2 | 1.386 (2) | C15—C16 | 1.3871 (19) |
C1—C6 | 1.405 (2) | C15—C20 | 1.3921 (19) |
C1—H1 | 0.9500 | C16—C17 | 1.3893 (19) |
C2—C3 | 1.386 (2) | C16—H16 | 0.9500 |
C2—H2 | 0.9500 | C17—C18 | 1.389 (2) |
C3—C4 | 1.381 (2) | C17—H17 | 0.9500 |
C3—H3 | 0.9500 | C18—C19 | 1.395 (2) |
C4—C5 | 1.392 (2) | C18—C21 | 1.5064 (19) |
C4—H4 | 0.9500 | C19—C20 | 1.387 (2) |
C5—C6 | 1.3984 (19) | C19—H19 | 0.9500 |
C6—C7 | 1.4647 (18) | C20—H20 | 0.9500 |
C7—C8 | 1.3581 (19) | C21—H21A | 0.9800 |
C8—C9 | 1.427 (2) | C21—H21B | 0.9800 |
C8—H8 | 0.9500 | C21—H21C | 0.9800 |
C9—C10 | 1.344 (2) | | |
| | | |
O2—S—O3 | 120.06 (7) | O1—C10—C11 | 116.69 (12) |
O2—S—N | 105.61 (7) | N—C11—C10 | 111.65 (11) |
O3—S—N | 106.13 (6) | N—C11—H11A | 109.3 |
O2—S—C15 | 107.81 (7) | C10—C11—H11A | 109.3 |
O3—S—C15 | 108.87 (7) | N—C11—H11B | 109.3 |
N—S—C15 | 107.76 (6) | C10—C11—H11B | 109.3 |
C10—O1—C7 | 106.97 (10) | H11A—C11—H11B | 108.0 |
C12—N—C11 | 114.90 (11) | C13—C12—N | 113.20 (11) |
C12—N—S | 116.88 (9) | C13—C12—H12A | 108.9 |
C11—N—S | 115.92 (9) | N—C12—H12A | 108.9 |
C2—C1—C6 | 121.79 (14) | C13—C12—H12B | 108.9 |
C2—C1—H1 | 119.1 | N—C12—H12B | 108.9 |
C6—C1—H1 | 119.1 | H12A—C12—H12B | 107.8 |
C3—C2—C1 | 120.15 (14) | C14—C13—C12 | 177.16 (16) |
C3—C2—H2 | 119.9 | C13—C14—H14 | 180.0 |
C1—C2—H2 | 119.9 | C16—C15—C20 | 120.68 (12) |
C4—C3—C2 | 119.51 (13) | C16—C15—S | 119.96 (10) |
C4—C3—H3 | 120.2 | C20—C15—S | 119.26 (10) |
C2—C3—H3 | 120.2 | C15—C16—C17 | 119.06 (13) |
C3—C4—C5 | 120.11 (14) | C15—C16—H16 | 120.5 |
C3—C4—H4 | 119.9 | C17—C16—H16 | 120.5 |
C5—C4—H4 | 119.9 | C18—C17—C16 | 121.48 (13) |
C4—C5—C6 | 121.84 (13) | C18—C17—H17 | 119.3 |
C4—C5—Cl | 116.63 (11) | C16—C17—H17 | 119.3 |
C6—C5—Cl | 121.53 (11) | C17—C18—C19 | 118.39 (13) |
C5—C6—C1 | 116.57 (12) | C17—C18—C21 | 120.62 (13) |
C5—C6—C7 | 124.60 (12) | C19—C18—C21 | 120.99 (13) |
C1—C6—C7 | 118.82 (12) | C20—C19—C18 | 121.10 (13) |
C8—C7—O1 | 109.21 (11) | C20—C19—H19 | 119.5 |
C8—C7—C6 | 136.62 (13) | C18—C19—H19 | 119.5 |
O1—C7—C6 | 114.11 (11) | C19—C20—C15 | 119.28 (13) |
C7—C8—C9 | 106.76 (13) | C19—C20—H20 | 120.4 |
C7—C8—H8 | 126.6 | C15—C20—H20 | 120.4 |
C9—C8—H8 | 126.6 | C18—C21—H21A | 109.5 |
C10—C9—C8 | 107.10 (13) | C18—C21—H21B | 109.5 |
C10—C9—H9 | 126.4 | H21A—C21—H21B | 109.5 |
C8—C9—H9 | 126.4 | C18—C21—H21C | 109.5 |
C9—C10—O1 | 109.96 (12) | H21A—C21—H21C | 109.5 |
C9—C10—C11 | 133.18 (13) | H21B—C21—H21C | 109.5 |
| | | |
O2—S—N—C12 | 173.49 (9) | C8—C9—C10—O1 | 0.43 (18) |
O3—S—N—C12 | 45.01 (11) | C8—C9—C10—C11 | 175.35 (15) |
C15—S—N—C12 | −71.48 (11) | C7—O1—C10—C9 | −0.60 (16) |
O2—S—N—C11 | −46.05 (11) | C7—O1—C10—C11 | −176.45 (12) |
O3—S—N—C11 | −174.53 (9) | C12—N—C11—C10 | −63.52 (15) |
C15—S—N—C11 | 68.98 (11) | S—N—C11—C10 | 155.24 (10) |
C6—C1—C2—C3 | 0.4 (2) | C9—C10—C11—N | 128.92 (18) |
C1—C2—C3—C4 | −1.2 (2) | O1—C10—C11—N | −56.42 (16) |
C2—C3—C4—C5 | 1.0 (2) | C11—N—C12—C13 | −58.63 (15) |
C3—C4—C5—C6 | 0.0 (2) | S—N—C12—C13 | 82.22 (13) |
C3—C4—C5—Cl | 180.00 (12) | O2—S—C15—C16 | −147.00 (12) |
C4—C5—C6—C1 | −0.8 (2) | O3—S—C15—C16 | −15.27 (14) |
Cl—C5—C6—C1 | 179.18 (11) | N—S—C15—C16 | 99.43 (12) |
C4—C5—C6—C7 | 179.02 (13) | O2—S—C15—C20 | 36.72 (14) |
Cl—C5—C6—C7 | −0.99 (19) | O3—S—C15—C20 | 168.46 (12) |
C2—C1—C6—C5 | 0.6 (2) | N—S—C15—C20 | −76.85 (13) |
C2—C1—C6—C7 | −179.20 (14) | C20—C15—C16—C17 | −0.2 (2) |
C10—O1—C7—C8 | 0.53 (15) | S—C15—C16—C17 | −176.46 (11) |
C10—O1—C7—C6 | 178.12 (11) | C15—C16—C17—C18 | 1.1 (2) |
C5—C6—C7—C8 | −15.8 (3) | C16—C17—C18—C19 | −0.9 (2) |
C1—C6—C7—C8 | 164.06 (17) | C16—C17—C18—C21 | 178.91 (14) |
C5—C6—C7—O1 | 167.56 (12) | C17—C18—C19—C20 | −0.2 (2) |
C1—C6—C7—O1 | −12.62 (18) | C21—C18—C19—C20 | −179.97 (15) |
O1—C7—C8—C9 | −0.28 (17) | C18—C19—C20—C15 | 1.0 (2) |
C6—C7—C8—C9 | −177.07 (16) | C16—C15—C20—C19 | −0.8 (2) |
C7—C8—C9—C10 | −0.09 (18) | S—C15—C20—C19 | 175.46 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 0.95 | 2.74 | 3.479 (2) | 135 |
C4—H4···Clii | 0.95 | 3.13 | 3.974 (2) | 148 |
C12—H12B···O1iii | 0.99 | 2.71 | 3.679 (2) | 165 |
C14—H14···O2iv | 0.95 | 2.38 | 3.242 (2) | 150 |
C20—H20···Clv | 0.95 | 3.07 | 3.949 (2) | 154 |
C19—H19···Clvi | 0.95 | 3.05 | 3.865 (2) | 145 |
C21—H21A···O2iv | 0.98 | 2.80 | 3.620 (2) | 142 |
C21—H21B···Clvi | 0.98 | 3.08 | 4.016 (2) | 159 |
C16—H16···Cg2iii | 0.95 | 2.66 | 3.484 (2) | 145 |
C20—H20···C5v | 0.95 | 2.90 | 3.777 (2) | 154 |
C1—H1···C14vii | 0.95 | 2.78 | 3.694 (2) | 162 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z; (v) −x+1, −y+2, −z+1; (vi) x−1, y, z+1; (vii) x+1, y, z. |
Experimental details
| (Ia) | (Ib) |
Crystal data |
Chemical formula | C21H18ClNO3S | C21H18ClNO3S |
Mr | 399.87 | 399.87 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 140 | 140 |
a, b, c (Å) | 7.5309 (16), 9.5789 (14), 13.893 (2) | 7.6526 (13), 9.679 (2), 13.6308 (19) |
α, β, γ (°) | 80.234 (9), 82.252 (14), 73.959 (10) | 79.910 (13), 75.152 (13), 74.435 (12) |
V (Å3) | 945.1 (3) | 934.0 (3) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.34 |
Crystal size (mm) | 0.50 × 0.24 × 0.08 | 0.50 × 0.16 × 0.12 |
|
Data collection |
Diffractometer | SIEMENS SMART CCD diffractometer | SIEMENS SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.923, 0.974 | 0.921, 0.960 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19065, 5805, 4256 | 19124, 6133, 4738 |
Rint | 0.037 | 0.029 |
(sin θ/λ)max (Å−1) | 0.723 | 0.735 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.107, 1.03 | 0.041, 0.094, 1.04 |
No. of reflections | 5805 | 6133 |
No. of parameters | 246 | 246 |
H-atom treatment | H atom parameters constrained | H atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.40 | 0.36, −0.47 |
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 0.95 | 2.64 | 3.519 (2) | 153 |
C4—H4···Clii | 0.95 | 3.01 | 3.821 (2) | 144 |
C12—H12B···O1iii | 0.99 | 2.73 | 3.703 (2) | 169 |
C14—H14···O2iv | 0.95 | 2.41 | 3.227 (3) | 144 |
C17—H17···Cliii | 0.95 | 2.97 | 3.900 (2) | 165 |
C19—H19···Clv | 0.95 | 3.05 | 3.977 (2) | 166 |
C21—H21A···O2iv | 0.98 | 2.61 | 3.423 (2) | 140 |
C16—H16···Cg2iii | 0.95 | 2.60 | 3.457 (2) | 150 |
C20—H20···C5v | 0.95 | 2.86 | 3.733 (2) | 154 |
C1—H1···C14vi | 0.95 | 2.87 | 3.812 (2) | 174 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z; (v) −x+1, −y+2, −z+1; (vi) x+1, y, z. |
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O3i | 0.95 | 2.74 | 3.479 (2) | 135 |
C4—H4···Clii | 0.95 | 3.13 | 3.974 (2) | 148 |
C12—H12B···O1iii | 0.99 | 2.71 | 3.679 (2) | 165 |
C14—H14···O2iv | 0.95 | 2.38 | 3.242 (2) | 150 |
C20—H20···Clv | 0.95 | 3.07 | 3.949 (2) | 154 |
C19—H19···Clvi | 0.95 | 3.05 | 3.865 (2) | 145 |
C21—H21A···O2iv | 0.98 | 2.80 | 3.620 (2) | 142 |
C21—H21B···Clvi | 0.98 | 3.08 | 4.016 (2) | 159 |
C16—H16···Cg2iii | 0.95 | 2.66 | 3.484 (2) | 145 |
C20—H20···C5v | 0.95 | 2.90 | 3.777 (2) | 154 |
C1—H1···C14vii | 0.95 | 2.78 | 3.694 (2) | 162 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z; (iii) −x+1, −y+1, −z+1; (iv) x−1, y, z; (v) −x+1, −y+2, −z+1; (vi) x−1, y, z+1; (vii) x+1, y, z. |
The title compounds, (Ia) and (Ib), respectively, were prepared as test substrates for the gold-catalysed conversion of furans bearing terminal alkyne groups to highly substituted biaryl compounds (for background material see Hashmi et al., 2000). \sch
Compounds (Ia) and (Ib) have isomorphous crystal structures despite the different positions of the Cl substituents. The conformations of molecules (Ia) and (Ib) are very similar, differences of about 2° are found for the torsion angles about the N—C11 and C6—C7 bonds, while a difference of about 5° is found for the torsion angle about the C10—C11 bond. There is a short intramolecular contact distance of 2.65 Å between Cl and H8 in (Ib). This distance is considerably shorter than the H···Cl distances of about 2.85 to 3.15 Å generally observed for intermolecular C—H···Cl contacts. The widening of the C5—C6—C7 and C6—C7—C8 angles in (Ib) by amounts of 5 and 3°, respectively, compared to (Ia) shows the H8···Cl contact to be probably repulsive. This repulsion is balanced by resonance between the π systems of the furan ring and the adjacent phenyl ring. Atom C6 deviates 0.047 (3) Å from the furan plane in (Ib) and only 0.015 (3) Å in (Ia). Nevertheless the angle between the plane of the furan ring and the plane of the phenyl group attached to C7 is very similar in both compounds: 13.51 (7)° in (Ia) and 13.91 (7)° in (Ib).
The N atom is considerably non-planar: the sum of the three valence angles about N is 347.4 (1)° in (Ia) and 347.7 (1)° in (Ib). The S atom shows a significant displacement from the plane of the phenyl ring to which it is attached: 0.134 (5) Å in (Ia) and 0.110 (4) Å in (Ib). This out-of-plane deformation may result from intermolecular interactions.
The crystal packing of both compounds shows two distinct features, which are represented in Figs. 2 and 3, respectively. The ethynyl group is involved in a short C—H···O interaction with an H14···O2 distance of 2.41 Å in (Ia) and 2.38 Å in (Ib) (Tables 1 and 2), resulting in hydrogen-bonded chains of molecules parallel to the x axis (Fig. 2). The ethynyl group also acts as an acceptor of a weak C—H···π contact. The C1—H1···πethynyl contact points more closely to the terminal atom C14 than to the center of the ethynyl group. Similar π interactions involving ethynyl groups have been summarized by Desiraju & Steiner (1999). The molecules are connected parallel to the y axis by various intermolecular interactions (Fig. 3): two Cphenyl—H···πphenyl interactions: C16—H16···Cg2iii and C20—H20···C5v (Cg2 represents the centroid of the phenyl ring C1–C6), a weak C—H···O interaction: C12—H12B···O1iii and C—H···Cl interactions. The latter are different in (Ia) and (Ib); a C17—H17···Cliii and a C19—H19···Clv interaction is observed in (Ia) whereas a C20—H20···Clv interaction is observed in (Ib).
Both compounds show a number of additional intermolecular C—H···Cl interactions. A C4—H4···Clii interaction is found in both compounds. Due to the different positions of the Cl atoms, however, the intermolecular C4···Clii vectors differ considerably in (Ia) and (Ib). Two further C—H···Cl interactions occur in (Ib): C19—H19···Clvi and C21—H21B···Clvi. Corresponding interactions are missing in (Ia). The isomorphism of (Ia) and (Ib) suggests that the crystal packing of (Ia) and (Ib) is determined by the intermolecular C—H···O and C—H···π interactions, rather than by the intermolecular C—H···Cl interactions. The minor importance of the latter interactions is in agreement with the observation by Aullón et al. (1998) that the Cl—C group is a very poor hydrogen-bond acceptor. The C—H···Cl contacts observed in (Ia) and (Ib) are rather long, with H···Cl distances between 2.97 and 3.13 Å. An inspection of 329 randomly selected chlorophenyl-containing structures from the CSD shows that the majority of intermolecular C—H···Cl contacts have H···Cl distances around 3.0 Å. With a few exceptions there are no intermolecular C—H···Cl contacts with H···Cl distances shorter than 2.8 Å. These contacts may be characterized as weak, electrostatic interactions rather than weak hydrogen bonds. The different positions of the Cl atoms in (Ia) and (Ib) result in small variations of the crystal packing, leading to significant differences in the lattice constants of (Ia) and (Ib). The largest difference is observed for the β values.